Quaternary, copolymeric, high molecular weight ammonium salts based on acrylic compounds, their preparation, and their use in cosmetics

ABSTRACT

Novel copolymeric ammonium salts which are soluble or form microemulsions in aqueous surfactant systems and which can be obtained by water-in-oil emulsion polymerization or solution polymerization of a quaternary ammonium salt of the acrylic acid series and at least one other acrylic comonomer and reaction with an anionic optionally zwitterionic surfactant, ion exchange taking place, and has a molecular weight distribution of 10 4  to 10 9 , the molecular weight of at least 5 percent by weight of the copolymer being 10 7  to 10 9 , can be used as cosmetics, in particular as hair cosmetics, hair treated according to the invention having excellent ease of dry combing and, in particular, ease of wet combing.

The present invention relates to copolymeric, quaternary ammonium saltswhich are soluble or give microemulsions in aqueous surfactant systems,and which have a molecular weight distribution of 10⁴ to 10⁹, themolecular weight of at least 5 percent by weight of the copolymer being10⁷ to 10⁹, and contain, in any order, recurring structural elements ofthe formulae ##STR1## in which A₁, A₂, A₃ and A₄ are each hydrogen ormethyl, G₁ and G₂ differ from one another and are each --CN, --COOH or##STR2## D₁ and D₂ are each oxygen or --NH--, E₁ and E₂ are eachalkylene having 1 to 4 carbon atoms and which is unsubstituted orsubstituted by hydroxyl, R₁, R₂, R₃ and R₄ are each methyl or ethyl, Qis alkyl or hydroxyalkyl having 1 to 4 carbon atoms or benzyl andX.sup.⊖ is the radical of at least one anionic surfactant, which may bezwitterionic.

The invention also relates to the preparation process for theabovementioned copolymeric ammonium salts, their use in cosmetics, thecosmetics (hair cosmetics) which contain the ammonium salts according tothe invention and methods of applying these cosmetics, in particularmethods of treating hair, and hair treated by these methods, for examplehair in the form of wigs.

The ammonium salts according to the invention are distinguished by thefact that they can be obtained by water-in-oil emulsion polymerisationor solution polymerisation of a quaternary ammonium salt of the acrylicacid series and at least one other acrylic comonomer, isolation of thecopolymer and reaction thereof with an anionic surfactant, which may bezwitterionic, ion exchange taking place.

The water-in-oil emulsion polymerisation, which is also called inverseemulsion polymerisation, or solution polymerisation, achieves the highmolecular weight range of 10⁷ to 10⁹ for the copolymers according to theinvention; within the wide molecular weight distribution of 10⁴ to 10⁹,preferably 5 to 60 and in particular 20 to 50 percent by weight of thecopolymers are within this high molecular weight range.

Most preferably, 30 to 45 percent by weight of the copolymers are withina molecular weight range of 10⁷ to 10⁹ and less than 15 percent byweight are in a molecular weight range smaller than 10⁵.

As well as providing the molecular weight distribution, the content ofstructural elements of the formula (1) in the copolymers, which is alsocalled the quaternary content, is another essential characteristic ofthe ammonium salts according to the invention, these salts containing onaverage about 5 to 80, preferably 6 to 40 and in particular 10 to 30,mol % of structural elements of the formula (1), on average about 10 to95, preferably 50 to 90, mol % of structural elements of the formula (2)and about 0 to 10 mol % of structural elements of the formula (3) and,optionally, (4), i.e. (3) and/or (4). Preferably, the copolymers containno structural elements of the formulae (3) and (4). However, in caseswhere such structural elements are present, the copolymers contain about1 to 8 mol % of structural elements of the formulae (3) and/or (4), andin particular in each case 1 to 4 mol % of the formulae (3) and (4).

In the formula (1), A₁ is preferably methyl, D₁ is preferably oxygen, E₁is preferably unsubstituted n-propyl or, in particular, unsubstitutedethylene, R₁ and R₂ are preferably methyl and Q is preferablyunsubstituted n-propyl, but preferably ethyl or, in particular, methyl.A₂ in formula (2) is preferably hydrogen. In formula (3), in cases wherestructural elements of the formula (3) are present by themselves, i.e.if no structural elements of the formula (4) are present, A₃ ispreferably methyl and G₁ is preferably ##STR3## in which D₂, E₂, R₃ andR₄ are the radicals defined above as preferred for D₁, E₁, R₁ and R₂. Incases where structural elements of the formula (4) are present inaddition to the structural elements of the formula (3), A₄ in formula(4) is preferably hydrogen and G₂ is preferably --CN or, in particular,--COOH.

Anionic, but not zwitterionic surfactant radicals X.sup.⊖ in formula (1)are preferably radicals of surface-active sarcosinates, sulfates, forexample alkyl-sulfates, alkyl ether-sulfates, alkylamide-sulfates,alkylamide ether-sulfates, alkylaryl polyether-sulfates ormonoglyceride-sulfates, sulfonates, for example alkylsulfonates,alkylamide-sulfonates, alkylarylsulfonates or α-olefinsulfonates, orsulfosuccinic acid derivatives, for example alkylsulfosuccinates, alkylether-sulfosuccinates, alkylamide-sulfosuccinates, alkylamidepolyether-sulfosuccinates or alkyl sulfosuccinamides, and also radicalsof fluorinated surfactants or phosphate surfactants, for example alkylphosphates or alkyl ether-phosphates.

X.sup.⊖ is, for example, a sarcosinate radical of the formula ##STR4##in which T₁ is alkyl or alkenyl having 7 to 21, preferably 11 to 17,carbon atoms.

The radicals T₁ CO-- are derived from the corresponding saturated orunsaturated fatty acids having 8 to 22, preferably 12 to 18, carbonatoms. Examples of the corresponding fatty acids are caprylic, capric,arachic and behenic acid, and in particular lauric, myristic, palmiticand stearic acid, or myristoleic, palmitoleic, elaeostearic andclupanodonic acid, and in particular oleic, elaidic, erucic, linoleicand linolenic acid. Alkyl and alkenyl radicals T₁ which are derived fromindustrial mixtures of the saturated and/or unsaturated fatty acidsmentioned are particularly preferred. Specific representatives ofsarcosinate radicals X.sup.⊖ are, in particular, the radicals of theformulae ##STR5##

Examples of sulfate radicals X.sup.⊖ (from alkylsulfates, and fromether-, ester-, amide- or amino-sulfates) are, in particular, radicalsof the formulae ##STR6## in which T₁ is as defined and T₂ is alkylhaving 6 to 14 carbon atoms, p is an integer from 1 to 50, q is aninteger from 6 to 12 and r is an integer from 2 to 6.

T₂ is preferably n-hexyl, n-heptyl, i-octyl, n-octyl, n-nonyl, orn-decyl, or lauryl or myristyl.

Specific representatives of sulfate radicals are, in particular, theradicals of the formulae ##STR7##

Sulfonate radicals X.sup.⊖ are radicals of the formulae ##STR8## inwhich T₁, T₂ and r are as defined, T₁ ' is the radical as defined forT₁, T₁ and T₁ ' being identical or different, and t is 1 or 2.

Specific representatives of such sulfonate radicals X.sup.⊖ are, inparticular, the radicals of the formulae ##STR9##

A sulfosuccinic acid derivative radical X.sup.⊖ is, for example, aradical of the formula ##STR10## in which T₁, T₂, p and t are as definedand T₂ ' is the radical as defined for T₂, T₂ and T₂ ' being identicalor different.

Specific representatives of such radicals X.sup.⊖ are the sulfosuccinicacid derivative radicals of the formulae ##STR11##

Fluorinated surfactant radicals X.sup.⊖ are, in particular, radicals ofthe formula ##STR12## in which T₃ is perfluorinated alkyl or alkenylhaving 6 to 14 carbon atoms.

A possible example of such radicals is the perfluorinated surfactantradical of the formula ##STR13##

Phosphate surfactant radicals X.sup.⊖ are, in particular, surfactantradicals of the formulae ##STR14## in which M is hydrogen, ammonium, analkali metal or alkyl having 1 to 3 carbon atoms, T₁, T₂, T₂ ', p and tare as defined and p' is the integer as defined for p, p and p' beingidentical or different.

Examples of such phosphate surfactant radicals are the radicals of theformulae ##STR15## and mixtures thereof, for example industrial mixturesof phosphate surfactant radicals of the formulae (52) and (53).

Zwitterionic anionic surfactant radicals X.sup.⊖ in formula (1) aresurfactant radicals which as a rule have one positive and two negativecharges, i.e. ampholytic surfactant radicals which always have an excessof negative charges. Radicals of such zwitterionic anionic surfactantsare, in particular, radicals of surface-activeN-alkyl-α-iminodipropionates, and especially imidazolinium-dicarboxylicacid derivatives which are alkyl-substituted in the 2-position.

Radicals of alkyl-substituted iminodipropionates are preferably those ofthe formula ##STR16## in which T₂ is as defined.

A specific example is the radical of the formula ##STR17##

The preferred imidazolinium radicals of the type mentioned are, inparticular, radicals of the formula ##STR18## in which T₂ is as defined.Specific examples are the radicals of the formulae ##STR19## andindustrial mixtures thereof.

Radicals X.sup.⊖ in formula (1) which are of particular interest areradicals of surface-active sarcosinates, sulfates, sulfonates,sulfosuccinic acid derivatives and imidazolinium-dicarboxylic acidderivatives, and especially the surfactant radicals of the formulae (7),(15), (16), (18), (27), (28), (43), (57) and (58).

The copolymeric, quaternary ammonium salts according to the inventioncan be prepared by methods known per se, for example water-in-oilemulsion polymerisation or solution polymerisation. In one preparationprocess, the comonomers of the formulae ##STR20## in which A₁, A₂, A₃,A₄, D₁, E₁, G₁, G₂, R₁, R₂ and Q are as defined and Y.sup.⊖ is a halideanion or an alkyl-sulfate or alkyl-phosphonate anion having 1 to 4carbon atoms in the alkyl radical, are copolymerised by water-in-oilemulsion polymerisation in the presence of a water-in-oil emulsifier andoptionally an emulsion stabiliser and a polymerisation initiator, andthe copolymer is precipitated with a solvent which is preferablymiscible with oil and water, for example methanol, acetone orisopropanol, and is then dried, the preparation process comprisingreacting the resulting copolymer with at least one anionic surfactant,which may be zwitterionic, of the formula

    X.sup.⊖ Z.sup.⊕                                ( 63)

in which Z.sup.⊕ is an alkali metal cation or an ammonium cation whichis unsubstituted or substituted by alkyl or alkanol radicals having 1 to4 carbon atoms and X.sup.⊖ is as defined, in an aqueous medium at 10° to60° C. and at a pH value of 5 to 9, the anion Y.sup.⊖ being replaced bythe anion X.sup.⊖.

If the solution polymerisation method is used, it is not necessary toemploy emulsifiers and emulsion stabilisers. Water is as a rule used asthe solvent.

Hydrophobic, organic liquids are required for the oil phase in thewater-in-oil emulsion polymerisation. Suitable oils for this purposeare, for example, aliphatic or aromatic hydrocarbons, oils of animal orvegetable origin and the corresponding denatured oils (for examplehydrogenated oils or polymerised oils). Preferred hydrophobic organicliquids are aliphatic hydrocarbons, such as kerosene, paraffin andisoparaffin, and aromatic hydrocarbons, such as benzene, toluene andxylene. Commercially available industrial mixtures of preferablybranched paraffin oils with a boiling range from 160° to 260° C.,preferably 180° to 210° C., are of particular interest.

Water-in-oil emulsifiers which are used in the inverse emulsionpolymerisation are polyoxyalkylene adducts, preferably polyoxyethyleneadducts, of aliphatic alcohols having 8 to 24 carbon atoms, such aslauryl, cetyl, stearyl and oleyl alcohol, of fatty acids of theabovementioned type having 8 to 24 carbon atoms, preferably lauric,palmitic, stearic and oleic acid, of alkylphenols having 8 to 24 carbonatoms in the alkyl radical, for example octyl-, nonyl-, dodecyl- anddinonyl-phenol, and of esters of fatty acids of the type mentioned andpolyhydric alcohols, for example glycerol, pentaerythritol, sorbitol andsorbitan. Commercially available mixtures, i.e. polyoxyalkylene adductsof industrial alcohol mixtures, fatty acid mixtures, alkylphenolmixtures and ester mixtures, are also particularly suitable for use aswater-in-oil emulsifiers. However, esters of fatty acids of the typementioned or of fatty acid mixtures and polyhydric alcohols of the typementioned are particularly preferred, sorbitan monooleate being ofspecial interest.

In particular cases, it has proved advantageous to use an emulsionstabiliser in the oil phase. Stabilisers which are suitable for thispurpose are, in particular, rubbers which are soluble in the oil phase,that is to say both rubbers of natural origin, for example crystal gum,and, preferably, those of synthetic origin, for example polybutadiene,styrene/butadiene copolymers and, in particular, polyisoprene.Polyisoprene is of special interest.

As a rule, the oil phase contains about 2 to 15 percent by weight ofemulsifier and 0 to about 1, preferably 0.4 to 0.8, percent by weight ofstabiliser.

After the oil phase has been mixed with the aqueous phase, whichcontains the comonomers of the formulae (59), (60) and optionally (61)and (62), the copolymerisation is as a rule started by adding apolymerisation initiator. The initiators employed can be the usualpolymerisation catalysts, preferably in the form of their aqueoussolutions, for example azo compounds, such as azo-bis(isobutyronitrile)or azo-bis(dimethylvaleronitrile), oxidising agents, preferablyperoxides, such as hydrogen peroxide or benzoyl peroxide, or,preferably, persulfates, such as ammonium persulfate, and also chloratesor chromates, reducing agents, such as sulfites, bisulfites, oxalic acidand ascorbic acid, and combinations of the abovementioned oxidising andreducing agents, as so-called redox catalysts. In the present case,sodium sulfite is a particularly suitable initiator.

The copolymerisation as a rule takes place at 30° to 90° C., preferably40° to 70° C., and can also proceed as an exothermic reaction, so thatit may be necessary to maintain the polymerisation temperature bycooling.

For usual working up of the product, the resulting copolymer is as arule precipitated by a solvent which is preferably miscible with oil andwater, for example methanol, isopropanol or acetone, the precipitationgenerally being carried out by adding the water-in-oil emulsion to thesolvent, preferably at room temperature (15° to 25° C.), after which thepolymer which has precipitated is filtered off and dried, preferably attemperatures of at most 60° C. and in particular at temperatures fromabout 30° to 50° C., reduced pressure being advantageous.

The resulting water-in-oil copolymers known per se are now converted bymethods known per se into the novel copolymeric quaternary ammoniumsalts according to the invention which contain structural elements ofthe formula (1). For this purpose, the resulting water-in-oil copolymersare reacted with the surfactant of the formula (63) as described above,the reaction preferably being carried out at temperatures from 15° to40° C. for 30 to 100, in particular 60 to 90, minutes. An excess of atleast one anionic surfactant, which may be zwitterionic, of the formula(63), based on the comonomeric quaternary ammonium salt of the formula(59) used in the preparation of the copolymer, is as a rule employed.This excess is about 4 to 500, preferably 5 to 120 and in particular 7to 70, mols of surfactant per mol of the monomeric ammonium salt used.

When used in the cosmetics industry, the novel, copolymeric quaternaryammonium salts according to the invention are preferably employed ashair cosmetics.

The cosmetics, preferably hair cosmetics, according to the invention asa rule contain an excess of at least one of the anionic surfactants,which may be zwitterionic, of the formula (63) used in the preparationof the ammonium salts, in addition to the novel copolymeric quaternaryammonium salts.

In their preferred embodiment, the cosmetics are in the form of aqueoushair cosmetics which contain 0.05 to 1.5, preferably 0.2 to 1.0, partsby weight, calculated as effective substance, of at least one polymericammonium salt having structural elements of the formula (1), (2), andoptionally (3) and/or (4), 5 to 20, preferably 8 to 15 and in particular9 to 12, parts by weight, calculated as effective substance, of at leastone anionic surfactant, which may be zwitterionic, of the formula (63)and optionally cosmetic assistants, and are diluted to a total of 100parts by weight with demineralised water.

The cosmetic assistants which may be present are commercially availableagents such as are used in hair cosmetics. These agents are, forexample, surfactants other than the surfactants of the formula (63),such as polyglycerol esters of fatty acids, in particular polyglycerololeates, or soaps, in particular the stearates of sodium, aluminium,magnesium, zinc or calcium, foam stabilisers, for example fatty acidpolyalkanolamides, thickeners of natural or synthetic origin, such ashydroxypropylmethylcellulose and polyacrylic acid, opalising agents,such as fatty acid monoalkanolamides or, preferably, glycerolmonostearate, and also, inter alia, preservatives, perfumes andpearlescent agents.

If required, the hair cosmetics are adjusted to a pH value of 5 to 8,preferably 7.0 to 7.5, or, even more preferably, 7.0 to 7.2 which canadvantageously be achieved by addition of, inter alia, an aqueoussolution of, for example, sodium hydroxide or citric acid.

When the aqueous hair cosmetic described above is used for hairtreatment, preferably on human hair, it is applied to hair which hasbeen wetted with tapwater, as a rule at room temperature or slightlyelevated temperature, for example 20° to 40° C., and the hair is thenshampooed and conditioned. The hair treated in this way can also be inthe form of wigs or toupees.

The essential advantage of the present invention is that application ofthe hair cosmetics which contain copolymeric quaternary ammonium saltshaving structural elements of the formula (1) comprising thecorresponding water-in-oil copolymers with high molecular weightcomponents and surfactants of the formula (63) gives the treated hairexcellent combing properties when dry and, in particular, when wet. Inparticular, the ease of wet combing of hair treated with the haircosmetics according to the invention is clearly superior to that of hairtreated with conventional cosmetics. The latter indeed also containmixtures and/or reaction products of surfactants and copolymers, but thecopolymers have a different composition and, in particular, they lackthe high molecular weight components.

In the preparation instructions and examples which follow, parts andpercentages are by weight.

Preparation instructions for water-in-oil emulsion copolymersInstructions A

The following three solutions are prepared in an oxygen-free, inertnitrogen atmosphere:

Solution I (oil phase)

500 parts of a branched paraffin oil (industrial mixture, molecularweight: 171, boiling range: 188°-206° C.) are introduced into adouble-walled reaction vessel. 140 parts of a 2.5% solution of asynthetic polyisoprene rubber (emulsion stabiliser) in paraffin oil ofthe type described and then 78 parts of sorbitan monooleate(water-in-oil emulsifier) are added to the paraffin oil at 20° C., withstirring.

A clear, yellowish solution is obtained.

Solution II (aqueous phase)

568.6 parts (8 mols) of acrylamide are dissolved in 700 parts ofdemineralised, oxygen-free water at 20° C. 220 parts of sodium chlorideare introduced into this solution, with stirring, and 1,133.2 parts of a50% aqueous solution of methacryloyloxyethyl-trimethylammoniummethyl-sulfate (2 mols) are then added.

A clear, colourless solution is obtained.

Solution III (initiator solution)

0.66 part of sodium sulfite are dissolved in 40 parts of demineralised,oxygen-free water.

Copolymerisation reaction

Solution II is added to solution I at 20° C. in an inert nitrogenatmosphere in the course of 10 minutes, with intensive stirring (3,000rpm). A homogeneous, white emulsion is obtained, and stirring iscontinued at 20° C. until the viscosity of a sample of the emulsion is14,000 mPa.s (Brookfield Viscosimeter LV, spindle 3, 6 rpm, 25° C.),which generally takes 10 minutes. Thereafter, the reaction mixture isheated to 40° C. in the course of 30 minutes, with stirring at 300 rpm.Solution III is now added to the reaction mixture by means of a meteringpump in the course of 150 minutes, the temperature being kept at 40° to41° C. by cooling. When the initiator solution has been added, stirringof the reaction mixture is continued at 40° C. and 300 rpm until theviscosity of a sample of the emulsion has fallen to 7,600 mPa.s(Brookfield Viscosimeter LV, spindle 1, 60 rpm, 25° C.), which generallytakes one hour.

Working up

The resulting emulsion of the copolymer is poured into 24,000 parts ofacetone at 20° C., with stirring, and the copolymer is precipitated. Theprecipitate is filtered off and dried at 40° C. under reduced pressurefor 2 days. 1,100 parts of a copolymer which contains, in any order, 80mol % of structural elements of the formula ##STR21## and 20 mol % ofstructural elements of the formula ##STR22## are obtained. 37% of thecopolymer has a molecular weight between 10⁷ and 10⁹.

Instructions B

The procedure described in instructions A is repeated, using 1,108 partsof a 40% aqueous solution of methacryloyloxypropyl-trimethylammoniumchloride (2 mols) in the aqueous phase (solution II).

1,000 parts of a copolymer which contains, in any order, 80 mol % ofstructural elements of the formula (64) given in instructions A and 20mol % of structural elements of the formula ##STR23## are obtained. 27%of the copolymer has a molecular weight between 10⁷ and 10⁹.

Instructions C

The procedure described in instructions A is repeated, using 1,622 partsof a 40% aqueous solution ofmethacryloyl-amidopropyl-diethyl-methylammonium methylsulfate (2 mols)in the aqueous phase (solution II).

648.8 parts of a copolymer which contains, in any order, 80 mol % ofstructural elements of the formula (64) given in instructions A and 20mol % of structural elements of the formula ##STR24## are obtained. 7%of the copolymer has a molecular weight between 10⁷ and 10⁹.

Instructions D

The procedure described in instructions A is repeated, using 1,471.5parts of a 40% aqueous solution ofmethacryloyloxypropyl-dimethyl-n-propylammonium bromide (2 mols) in theaqueous phase (solution II).

1,000 parts of a copolymer which contains, in any order, 80 mol % ofstructural elements of the formula (64) given in instructions A and 20mol % of structural elements of the formula ##STR25## are obtained. 22%of the copolymer has a molecular weight between 10⁷ and 10⁹.

Instructions E

The procedure described in instructions A is repeated, employing thefollowing solutions I, II and III, and using 40,000 parts of acetone inthe working up operation.

Solution I

825 parts of the paraffin oil described in instructions A, 269 parts ofthe 2.5% rubber solution described in instructions A and 255 parts ofsorbitan monooleate.

Solution II

An aqueous solution of 681.6 parts (9.6 mols) of acrylamide, 34.6 parts(0.48 mol) of acrylic acid, 50.3 parts (0.32 mol) of ethyldimethylamino-methacrylate and 220 parts of sodium chloride in 700 partsof water, and an aqueous solution of 1,586.5 parts (5.6 mols) ofmethacryloyloxyethyl-trimethylammonium methyl-sulfate in 3,100 parts ofwater.

Solution III

1.07 parts of sodium sulfite in 66.8 parts of water.

2,100 parts of a copolymer which contains, in any order, 60 mol % ofstructural elements of the formula (64) given in instructions A, 35 mol% of structural elements of the formula (65) given in instructions A, 3mol % of structural elements of the formula ##STR26## and 2 mol % ofstructural elements of the formula ##STR27## are obtained. 12% of thecopolymer has a molecular weight between 10⁷ and 10⁹.

Instructions F

The procedure described in instructions A is repeated, employing thefollowing solutions I, II and III and using 50,000 parts of acetone inthe working up operation.

Solution I* 1,628 parts of the paraffin oil described in instructions Aand 191 parts of sorbitan monooleate. (* in contrast to instructions A,contains no rubber solution). Solution II

A solution of 1,516.6 parts (21.36 mols) of acrylamide**, 679.9 parts(2.40 mols) of methacryloyloxyethyl-trimethylammonium methyl-sulfate,37.7 parts (0.24 mol) of ethyl dimethylamino-methacrylate** and 600parts of sodium chloride** in 2,550 parts of water. (** in contrast toinstructions A, these components are not added separately).

Solution III

1.6 parts of sodium sulfite and 720 parts of water.

1,890 parts of a copolymer which contains, in any order, 90 mol % ofstructural elements of the formula (64) given in instructions A, 9 mol %of structural elements of the formula (65) given in instructions A and 1mol % of structural elements of the formula (70) given in instructionsE, are obtained. 23% of the copolymer has a molecular weight between 10⁷and 10⁹.

Preparation instructions for a solution copolymer Instructions G

The following two solutions are prepared in an oxygen-free inertnitrogen atmosphere:

Solution 1 (monomer solution)

71.1 parts (1 mol) of acrylamide and 141.7 parts of a 50% aqueoussolution of methacryloyloxyethyltrimethylammonium methyl-sulfate (0.25mol) are dissolved in 228 parts of demineralised, oxygen-free water in adouble-walled vessel at 20° C.

A clear colourless solution is obtained.

Solution II (initiator solution)

0.2 part of ammonium peroxodisulfate are dissolved in 150 parts ofdemineralised, oxygen-free water.

Copolymerisation reaction

Half of solution II is added to solution I at 35° C. in an inertnitrogen atmosphere in the course of 1 minute, with stirring. After 6hours, the reaction solution is warmed to 50° C. and the second half ofsolution II is added. The mixture is stirred for 2 to 3 hours until ahighly viscous solution has formed. The reaction mixture is left tostand, without stirring. After 24 hours, the resulting colourless gel isallowed to cool.

Working up

The gel is comminuted, and dissolved in 1,350 parts of demineralisedwater. The highly viscous solution is then extruded as a thin strand at20° C. into 18,000 parts of acetone, and the copolymer is precipitated.It is then filtered off and kneaded again in 1,800 parts of acetoneuntil it becomes hard and brittle. It is again filtered off, and isdried under reduced pressure at 40° C. for 2 days. 110 parts of acopolymer which contains, in any order, 80 mol % of structural elementsof the formula ##STR28## and 20 mol % of structural elements of theformula ##STR29## are obtained. 12% of the copolymer has a molecularweight between 10⁷ and 10⁹.

EXAMPLE 1

100 parts of an aqueous solution containing 1.71 parts of the copolymeraccording to instructions A (3 m-equivalents, based on the quaternarycontent of the copolymer) are added to a solution of 24.9 parts of thesurfactant of the formula (71) CH₃ -(CH₂)₁₁ -O-SO₃ H.N(CH₂ -CH₂ OH)₃ (70mmols or 23.3 mols per mol of the comonomeric, quaternary ammonium saltused in instructions A) in 150 parts of water at 35° C. in the course of80 minutes, reaction of the quaternary structural elements of thecopolymer with the surfactant employed simultaneously taking place, withion exchange. 250 parts of an aqueous, slightly opalescent, viscoussolution containing 9.5% of surfactant of the abovementioned formula(71) and 0.9% of a copolymer which comprises, in any order, 80 mol % ofstructural elements of the formula (64) given in instructions A and 20mol % of structural elements of the formula ##STR30## are obtained.

EXAMPLE 2

The procedure described in Example 1 is repeated, using 7.7 parts of thesurfactant of the formula ##STR31## (20 mmols or 6.67 mols per mol ofthe comonomeric, quaternary ammonium salts used in instructions A).

250 parts of an aqueous, slightly opalescent solution containing 2.6% ofsurfactant of the abovementioned formula (73) and 1.0% of a copolymerwhich comprises, in any order, 80 mol % of structural elements of theformula (64) given in instructions A and 20 mol % of structural elementsof the formula ##STR32## are obtained.

EXAMPLE 3

The procedure described in Example 1 is repeated, using 29.3 parts ofthe surfactant of the formula ##STR33## (100 mmols or 33.3 mols per molof the comonomeric, quaternary ammonium salt used in instructions A).250 parts of an aqueous, slightly opalescent viscous solution containing11.3% of the surfactant of the abovementioned formula (75) and 0.9% of acopolymer which comprises, in any order, 80 mol % of structural elementsof the formula (64) given in instructions A and 20 mol % of structuralelements of the formula ##STR34## are obtained.

EXAMPLE 4

The procedure described in Example 1 is repeated, using 25.7 parts ofthe surfactant of the formula ##STR35## (50 mmols or 16.7 mols per molof the comonomeric, quaternary ammonium salt used in instructions A).

250 parts of an aqueous, slightly opalescent solution containing 9.7% ofsurfactant of the abovementioned formula (77) and 1.1% of a copolymerwhich comprises, in any order, 80 mol % of structural elements of theformula (64) given in instructions A and 20 mol % of structural elementsof the formula ##STR36## are obtained.

EXAMPLE 5

The procedure described in Example 1 is repeated, using 25.2 parts ofthe surfactant of the formula ##STR37## (60 mmols or 20 mols per mol ofthe comonomeric, quaternary ammonium salt used in instructions A).

250 parts of an aqueous, slightly opalescent solution containing 9.6% ofsurfactant of the abovementioned formula (79) and 1.1% of a copolymerwhich comprises, in any order, 80 mol % of structural elements of theformula (64) given in instructions A and 20 mol % of structural elementsof the formula ##STR38## are obtained.

EXAMPLE 6

The procedure described in Example 1 is repeated, using 24.4 parts ofthe surfactant of the formula ##STR39## (70 mmols or 22.3 mols per molof the comonomeric, quaternary ammonium salt used in instructions A).

250 parts of an aqueous, slightly opalescent solution containing 9.3% ofsurfactant of the abovementioned formula (81) and 0.85% of a copolymerwhich comprises, in any order, 80 mol % of structural elements of theformula (64) given in instructions A and 20 mol % of structural elementsof the formula ##STR40## are obtained.

EXAMPLE 7

100 parts of an aqueous solution containing 2.02 parts of the copolymeraccording to instructions B (4 mequivalents, based on the quaternarycontent of the copolymer) are added to a solution of 105 parts of thesurfactant of the formula (79) given in Example 5 (250 mmols or 62.5mols per mol of the comonomeric, quaternary ammonium salt used ininstructions B) in 900 parts of water at 25° C. in the course of 1 hour,the reaction of the quaternary structural elements of the copolymer withthe surfactant employed simultaneously taking place, with ion exchange.1,000 parts of an aqueous, slightly opalescent, viscous solutioncontaining 10.4% of surfactant of the abovementioned formula (79) and0.31% of a copolymer which comprises, in any order, 80 mol % ofstructural elements of the formula (64) given in instructions A and 20mol % of structural elements of the formula (80) given in Example 5 areobtained.

EXAMPLE 8

The procedure described in Example 7 is repeated, using 104 parts of thesurfactant of the formula (71) given in Example 1 (250 mmols or 62.5mols per mol of the comonomeric, quaternary ammonium salt used ininstructions B).

1,000 parts of an aqueous, slightly opalescent solution containing 10.3%of the surfactant of the abovementioned formula (71) and 0.3% of acopolymer which comprises, in any order, 80 mol % of structural elementsof the formula (64) given in instructions A and 20 mol % of structuralelements of the formula (72) given in Example 1, are obtained.

EXAMPLE 9

10 parts of an aqueous solution containing 0.168 part of the copolymeraccording to instructions E (0.4 m-equivalent, based on the quaternarycontent of the copolymer) are added to a solution of 10.5 parts of thesurfactant of the formula (71) given in Example 1 (5.71 mmols or 14.3mols per mol of the comonomeric ammonium salt used in instructions E) in90 parts of water at 35° C. in the course of 90 minutes, the reaction ofthe quaternary structural elements of the copolymer with the surfactantemployed simultaneously taking place, with ion exchange. 100 parts of anaqueous, slightly opalescent, viscous solution containing 9.8% ofsurfactant of the above-mentioned formula (71) and 0.38% of a copolymerwhich comprises, in any order, 60 mol % of structural elements of theformula (64) given in instructions A, 3 mol % of structural elements ofthe formula (69) given in instructions E, 2 mol % of structural elementsof the formula (70) given in instructions E and 35 mol % of structuralelements of the formula (72) given in Example 1, are obtained.

EXAMPLE 10

35 parts of an aqueous solution containing 0.65 part of the copolymeraccording to instructions E (0.7 m-equivalent, based on the quaternarycontent of the copolymer) are added to a solution of 13.7 parts of thesurfactant of the formula ##STR41## (40 mmols or 57.1 mols per mol ofthe comonomeric, quaternary ammonium salt used in instructions E) in 65parts of water at 30° C. in the course of 75 minutes, reaction of thequaternary structural elements of the copolymer with the surfactantemployed simultaneously taking place, with ion exchange.

100 parts of an aqueous, slightly opalescent, viscous solutioncontaining 13.5% of surfactant of the abovementioned formula (83) and0.75% of a copolymer which comprises, in any order, 90 mol % ofstructural elements of the formula (64) given in instructions A, 1 mol %of structural elements of the formula (69) given in instructions E and 9mol % of structural elements of the formula ##STR42## are obtained.

EXAMPLE 11

50 parts of an aqueous solution containing 0.58 part of the copolymeraccording to instructions D (1 m-equivalent, based on the quaternarycontent of the copolymer) are added to a solution of 11.6 parts of thesurfactant of the formula (73) given in Example 2 (30 mmols, i.e. 30mols per mol of the comonomeric quaternary ammonium salt used ininstructions D) in 50 parts of water at 45° C. in the course of 50minutes, reaction of the quaternary structural elements of the copolymerwith the surfactant employed simultaneously taking place, with ionexchange.

100 parts of an aqueous, slightly opalescent viscous solution containing11.2% of surfactant of the abovementioned formula (73) and 0.87% of acopolymer which comprises, in any order, 80 mol % of structural elementsof the formula (64) given in instructions A and 20 mol % of structuralelements of the formula ##STR43## are obtained.

EXAMPLE 12

The aqueous solution according to Example 1 is adjusted to a pH value of7.1 by addition of 10% aqueous citric acid solution, and is used totreat a wig, which has been wetted with tapwater, of unbleached, undyed,brown human hair of European origin by three applications in a so-calledhalf-head test at 30° C., after which the hair of the wig is shampooedand conditioned at this temperature. In the half-head test, one half ofthe wig is shampooed and conditioned with the solution described above,whilst the other half of the wig is shampooed under the same conditionsbut using a solution containing only surfactant and no copolymeraccording to the invention. In this so-called blank formulation, thecopolymer is replaced by the appropriate amount of surfactant, so that,for example in comparison with Example 1, the blank formulation contains10.4% of surfactant of the formula (71) given in Example 1, the pH valueof the blank formulation likewise being adjusted to 7.1 with aqueous 10%citric acid solution. After each application, the ease of wet and drycombing of the half of the wig treated according to the invention isevaluated in comparison with the half of the wig treated with the blankformulation, the following scale of ratings being used:

+3 much better than the blank formulation

+2 better than the blank formulation

+1 somewhat better than the blank formulation

0 no different to the blank formulation

-1 somewhat poorer than the blank formulation

-2 poorer than the blank formulation

-3 much poorer than the blank formulation.

The combing ratings achieved using the solution according to Example 1are summarised in Table I.

                  TABLE I                                                         ______________________________________                                                  after the after the after the                                                 1st       2nd       3rd                                                       application                                                                             application                                                                             application                                     ______________________________________                                        Wet combing rating                                                                        +2          +3        +3                                          Dry combing rating                                                                        +2          +(2-3)    +3                                          ______________________________________                                    

Similar results are achieved with the aqueous solution according toExample 3 and the corresponding blank formulation.

EXAMPLE 13

The procedure described in Example 12 is repeated, using the aqueoussolution according to Example 4 and the corresponding blank formulation.

The combing ratings achieved are summarised in Table II.

                  TABLE II                                                        ______________________________________                                                  after the after the after the                                                 1st       2nd       3rd                                                       application                                                                             application                                                                             application                                     ______________________________________                                        Wet combing rating                                                                        +(1-2)      +(1-2)    +(1-2)                                      Dry combing rating                                                                        +1          +(1-2)    +(1-2)                                      ______________________________________                                    

EXAMPLE 14

The procedure described in Example 12 is repeated, using the aqueoussolution according to Example 5 and the corresponding blank formulation.

The combing ratings achieved are summarised in Table III.

                  TABLE III                                                       ______________________________________                                                  after the after the after the                                                 1st       2nd       3rd                                                       application                                                                             application                                                                             application                                     ______________________________________                                        Wet combing rating                                                                        +(1-2)      +2        +2                                          Dry combing rating                                                                        +(0-1)      +(0-1)    +1                                          ______________________________________                                    

Similar results are achieved with the aqueous solutions according toExamples 6 and 7 and the corresponding blank formulations.

EXAMPLE 15

The procedure described in Example 12 is repeated, using the aqueoussolution according to Example 8 and the corresponding blank formulation.

The combing ratings achieved are summarised in Table IV.

                  TABLE IV                                                        ______________________________________                                                  after the after the after the                                                 1st       2nd       3rd                                                       application                                                                             application                                                                             application                                     ______________________________________                                        Wet combing rating                                                                        +(0-1)      +1        +1                                          Dry combing rating                                                                        +1          +(0-1)    +1                                          ______________________________________                                    

EXAMPLE 16

The procedure described in Example 12 is repeated, using the aqueoussolution according to Example 2 and the corresponding blank formulation.

The combing ratings achieved are summarised in Table V.

                  TABLE V                                                         ______________________________________                                                  after the after the after the                                                 1st       2nd       3rd                                                       application                                                                             application                                                                             application                                     ______________________________________                                        Wet combing rating                                                                        +1          +2        +(1-2)                                      Dry combing rating                                                                        +1          +2        +2                                          ______________________________________                                    

Similar results are achieved with the aqueous solution according toExample 8 and the corresponding blank formulation.

EXAMPLE 17

The procedure described in Example 12 is repeated, using the aqueoussolution according to Example 9 and the corresponding blank formulation.

The wet combing ratings achieved are +1 after the 1st application and ineach case +(1-2) after the 2nd and 3rd application.

EXAMPLE 18

The procedure described in Example 12 is repeated, using the aqueoussolution according to Example 10 and the corresponding blankformulation.

The combing ratings achieved are summarised in Table VI.

                  TABLE VI                                                        ______________________________________                                                  after the after the after the                                                 1st       2nd       3rd                                                       application                                                                             application                                                                             application                                     ______________________________________                                        Wet combing rating                                                                        +2          +2        +2                                          Dry combing rating                                                                        +1          +1        +1                                          ______________________________________                                    

Similar results are achieved with the aqueous solution according toExample 11 and the corresponding blank formulation.

EXAMPLE 19

100 parts of a copolymer comprising 74 mol % of structural elements ofthe formula (64) and 26 mol % of elements of the formula (65) arepulverised and the powder is stirred with a mixture of 400 parts ofmethanol and 100 parts of water at room temperature for 30 minutes. Afurther 500 parts of methanol are added and the mixture is stirred foranother 5 minutes and then left to stand for one hour. The gelatinoussludge is then filtered in a pressure filter under a pressure of 3 bars.The gelatinous mass is then suspended in 100 parts of methanol and thesuspension is filtered again under pressure. After three treatments withmethanol, the product is dried in vacuo at 40° C. for one day.

According to the values obtained by means of gel permeationchromatography, the molecular weight distribution in the startingpolymer (A) and in the polymer (B) treated in accordance with the aboveinstructions is as follows:

    ______________________________________                                        Polymer  M ≧ 10.sup.7                                                                       M = 10.sup.5 -10.sup.7                                                                   M < 10.sup.5                                  ______________________________________                                        A        20%         29%        51%                                           B        39%         48%        13%                                           ______________________________________                                    

Formulations of the two polymers A and B are prepared by the proceduredescribed in Example 1 by adding in each case a solution of 1.4 parts ofone of the two polymers in 80 parts of water to a solution of 20 partsof the compound of the formula CH₃ (CH₂)₁₁ OSO₃ H.N(CH₂ CH₂ OH)₃ in 120parts of water.

When these formulations are tested on wigs in the half-head test asdescribed in Example 12, they both give better ease of wet combingcompared with the blank formulation.

This effect, however, is more pronounced in the case of the formulationcontaining the purified polymer B.

    ______________________________________                                                 Wet combing rating                                                            after the after the after the                                                 1st       2nd       3rd                                                       application                                                                             application                                                                             application                                      ______________________________________                                        Formulation                                                                              + 1-2       +2        +2                                           containing                                                                    Polymer A                                                                     Formulation                                                                              +2          +3        +3                                           containing                                                                    Polymer B                                                                     ______________________________________                                    

What is claimed is:
 1. A copolymeric, quaternary ammonium salt which issoluble or forms a microemulsion in an aqueous surfactant system, whichhas a molecular weight distribution of 10⁴ to 10⁹, the molecular weightof at least 5 percent by weight of the copolymer being 10⁷ to 10⁹, andcomprises, in any order, recurring structural elements of the formulae##STR44## in which A₁ and A₂ are each hydrogen or methyl, D₁ is oxygenor --NH--, E₁ is alkylene having 1 to 4 carbon atoms unsubstituted orsubstituted by hydroxyl, R₁ and R₂ are each methyl or ethyl, Q is alkylor hydroxyalkyl having 1 to 4 carbon atoms or benzyl and X.sup.⊖ is theradical of at least one anionic sulfate ether surfactant, which may bezwitterionic.
 2. An ammonium salt according to claim 1, which isobtained by water-in-oil emulsion polymerisation or a solutionpolymerisation of a quaternary ammonium salt of the acrylic acid seriesand at least one other acrylic comonomer, isolation of the copolymer andreaction thereof with an anionic and optionally zwitterionic surfactant,ion exchange taking place.
 3. An ammonium salt according to claim 1,which contains on average 5 to 80 mol % of structural elements of theformula ##STR45## on average 10 to 95 mol % of structural elements ofthe formula ##STR46## in which A₁, A₂, D₁, E₁, R₁, R₂, Q and X.sup.⊖ areas defined in claim
 1. 4. An ammonium salt according to claim 1, inwhich the molecular weight of 5 to 60 percent by weight of the copolymeris 10⁷ to 10⁹.
 5. An ammonium salt according to claim 1, in whichX.sup.⊖ is a sulfur-ether radical of the formulae ##STR47## in which T₁is alkyl or alkenyl having 7 to 21 carbon atoms, T₂ is alkyl having 6 to14 carbon atoms, p is an integer from 1 to 50, q is an integer from 6 to12 and r is an integer from 2 to
 6. 6. A copolymeric, quaternaryammonium salt of claim 1 which is soluble or forms a microemulsion in anaqueous surfactant system, which has a molecular weight distribution of10⁴ to 10⁹, the molecular weight of at least 5 percent by weight of thecopolymer being 10⁷ to 10⁹, and which is obtained by water-in-oilemulsion polymerisation, in the presence of a water-in-oil emulsifierand, optionally, an emulsion stabiliser, or by solution polymerisation,in each case in the presence of a polymerisation initiator, ofcomonomers of the formulae ##STR48## in which A₁, A₂, D₁, E₁, Q, R₁ andR₂ are as defined in claim 1 and Y.sup.⊖ is a halide anion or analkyl-sulfate or alkyl-phosphonate anion having 1 to 4 carbon atoms inthe alkyl radical, subsequent precipitation of the copolymer with awater-soluble solvent, drying of the copolymer and reaction thereof withat least one surfactant of the formula

    X.sup.⊖ Z.sup.⊕

in which Z.sup.⊕ is an alkali metal cation or an ammonium cation whichis unsubstituted or substituted by alkyl or alkanol radicals having 1 to4 carbon atoms and X.sup.⊖ is as defined in claim 1, in an aqueousmedium at 10° to 60° C. and at a pH value of 5 to 9, the anion Y.sup.⊖being replaced by the anion X.sup.⊖.
 7. A cosmetic, which contains atleast one polymeric ammonium salt according to claim
 1. 8. A cosmeticaccording to claim 7, which contains an excess of at least one of theanionic and optionally zwitterionic surfactants, of the formulaaccording to claim 16 used in the preparation of the ammonium salt.
 9. Acosmetic according to claim 7 which is a hair cosmetic.
 10. A haircosmetic according to claim 9, which contains 0.05 to 1.5 parts byweight, calculated as effective substance, of at least one polymericammonium salt according to any one of claims 1 to 5, 5 to 20 parts byweight, calculated as effective substance, of at least one anionic andoptionally zwitterionic surfactant, and, optionally, a cosmeticassistant and is diluted with demineralized water to a total of 100parts by weight.
 11. A hair cosmetic according to claim 10, which isadjusted to a pH value of 7.0 to 7.5 with an aqueous solution of sodiumhydroxide or citric acid.
 12. A method of hair treatment to give ease ofwet and dry combing which comprises the step of applying a cosmeticwhich contains at least one copolymeric, quaternary ammonium salt whichis soluble or forms a microemulsion in an aqueous surfactant system,which has a molecular weight distribution of 10⁴ to 10⁹, the molecularweight of at least 5 percent by weight of the copolymer being 10⁷ and10⁹, and comprises, in any order, recurring structural elements of theformulae ##STR49## in which A₁ and A₂ are each hydrogen or methyl, D₁ isoxygen or --NH--, E₁ is alkylene having 1 to 4 carbon atomsunsubstituted or substituted by hydroxyl, R₁ and R₂ are each methyl orethyl, Q is alkyl or hydroxyalkyl having 1 to 4 carbon atoms or benzyland X.sup.⊖ is the radical of at least one anionic sulfate ethersurfactant, which may be zwitterionic.
 13. The method of claim 12wherein the cosmetic contains 0.05 to 1.5 parts by weight, calculated aseffective substance, of the polymeric ammonium salt, 5 to 20 parts byweight, calculated as effective substance, of at least one anionic andoptionally zwitterionic surfactant, and is diluted with demineralizedwater to a total of 100 parts by weight.
 14. The method of claim 13wherein the cosmetic is adjusted to a pH value of 7.0 to 7.5 with anaqueous solution of sodium hydroxide or citric acid.